Main Group Heterocycles from Lithiated Phosphinimines
Bibliographic record
Abstract
Reaction of the phosphinimines (Me) t Bu 2 PNSiMe 3 ( 1 ), (Me) t Bu 2 PNC 6 H 2 Me 3 ( 3 ), and (PhCH 2 ) t Bu 2 PNSiMe 3 ( 6 ) with n BuLi and subsequently (C 6 F 5 ) 2 BCl affords the four-membered heterocycles [((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNSiMe 3 ] ( 2 ), [((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNC 6 H 2 Me 3 ] ( 5 ), and [((C 6 F 5 ) 2 BCH(Ph)) t- Bu 2 PNSiMe 3 ] ( 7 ), respectively. The related phosphinimine ( i Pr) t Bu 2 PNSiMe 3 ( 8 ) reacts with t BuLi to give (LiCMe 2 ) t Bu 2 PNSiMe 3 ( 9 ), which reacts with (C 6 F 5 ) 2 BCl to yield the five-membered heterocycle [((C 6 F 5 ) 2 BCH 2 CH(Me)) t Bu 2 PNSiMe 3 ] ( 10 ). Similarly, the species [(Me 2 AlCMe 2 ) i Pr 2 PNSiMe 3 ] ( 12 ) and [((Me 2 N) 2 BCMe 2 ) i Pr 2 PNSiMe 3 ] ( 13 ) were prepared from lithiation of the phosphinimine i Pr 3 PNSiMe 3 ( 11 ). In exploring the chemistry of these heterocycles, compound 2 reacts with [Me 3 NH]Cl and MeOH to open the heterocycle, giving [(C 6 F 5 ) 2 B(Cl)CH 2 P t Bu 2 NH(SiMe 3 )] ( 14 ) and ((C 6 F 5 ) 2 B(OMe)CH 2 ) t Bu 2 PNH 2 ( 15 ), respectively. Subsequent treatment of 15 with Me 3 SiCl affords the species ((C 6 F 5 ) 2 B(Cl)CH 2 ) t Bu 2 PNH 2 ( 16 ), while treatment of 16 with n BuLi gives [((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNH)] ( 17 ). Compound 17 coordinates AlMe 3 to give ((C 6 F 5 ) 2 BCH 2 ) t Bu 2 PNH](AlMe 3 ) ( 18 ), while 15 reacts with AlMe 3 to give the six-membered heterocycle [((C 6 F 5 ) 2 B(OMe)CH 2 ) t Bu 2 PNH)(AlMe 2 )] ( 19 ). This chemistry is discussed and the implications are considered. X-ray crystallographic data are reported for 2, 5, 7, 9, 10, 14, and 17 .
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How this classification was reachedexpand
Full frame machine prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. The Gemma side is a direct model label for every work in the frame, read from the title-only record. The Codex side is a classifier learned from the 10,348 direct Codex labels and calibrated to design-weighted sample rates; fields without enough sample support carry no Codex call. Candidate is the union of the two sides; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels.
Distilled classifier scores by category (both heads)
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.001 | 0.000 |
| Research integrity | 0.000 | 0.001 |
| Insufficient payload (model declined to judge) | 0.006 | 0.001 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one source (direct Gemma or distilled Codex), not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".